Temperature-Driven Phase Evolution and Lattice Strain Dynamics During Ga–Sb Co-Diffusion in Single-Crystal Silicon
Abstract
This study examines the effect of annealing temperature on the microstructure and lattice dynamics of single-crystal silicon co-diffused with gallium and antimony. Samples were annealed in the 1000–1250°C range for a fixed duration of 10 h and analyzed by SEM imaging, EDS elemental mapping, and Raman spectroscopy. With increasing temperature, the samples show four successive microstructural states: (I) sparse Ga-rich clustering at 1000°C, (II) formation of large GaSb droplets (25–60 µm) at 1100°C, (III) refinement into smaller, faceted precipitates (~5 µm) at 1200°C, and (IV) substantial re-dissolution of the secondary phase, leaving only residual domains of ~1.5 µm, at 1250°C. Raman measurements of the Si optical phonon track this sequence: a small tensile shift (~518–519 cm⁻¹) at 1000 °C, a return to the unstrained position (~520 cm⁻¹) at 1100°C when GaSb droplets accommodate most of the lattice mismatch, and increasing compressive shifts (524–525 cm⁻¹, corresponding to ~0.6% strain) at 1200–1250°C as the GaSb phase redissolves into the matrix. Phonon-confinement analysis of the Raman linewidth further indicates crystalline coherence lengths of 3–5 nm within the micrometer-scale precipitates. Taken together, these results indicate that annealing temperature governs a reproducible sequence of clustering, droplet segregation, precipitate refinement, and re-homogenization in the Ga–Sb–Si system, and that this sequence can be tracked quantitatively through the correlated SEM/EDS and Raman signatures reported here.
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S.M. Sze, and K.K. Ng, Physics of Semiconductor Devices, 3rd ed., (Wiley, 2007). https://doi.org/10.1002/0470068329
C. Barri, E. Mafakheri, L. Fagiani, G. Tavani, A. Barzaghi, D. Chrastina, A. Fedorov, et al., “Engineering of the spin on dopant process on silicon on insulator substrate,” Nanotechnology, 32, 025303 (2021). https://doi.org/10.1088/1361-6528/abbdda
P.M. Fahey, P. B. Griffin, and J. D. Plummer, “Point defects and dopant diffusion in silicon,” Rev. Mod. Phys. 61, 289–384 (1989). https://doi.org/10.1103/RevModPhys.61.289
Y. Su, D. Saric, G. Guevara-Carrion, Y. Zhang, M. He, and J. Vrabec, “Fick and Maxwell-Stefan diffusion of the liquid mixture cyclohexane+toluene+ acetone+ methanol and its subsystems”, Chemical Engineering Science, 301, 120662 (2025). https://doi.org/10.1016/j.ces.2024.120662
M. Bonvalet-Rolland, T. Philippe, and J. Ågren, “Kinetic theory of nucleation in multicomponent systems: An application of the thermodynamic extremum principle”, Acta Materialia, 171(1), 1-7 (2019). https://doi.org/10.1016/j.actamat.2019.03.031
Kh.M. Iliev, N.F. Zikrillaev, K.S. Ayupov, B.O. Isakov, B.A. Abdurakhmanov, Z.N. Umarkhodjaeva, and L.I. Isamiddinova, “Effect of GaSb Compound on Silicon Bandgap Energy”, J. Nano- Electron. Phys. 16(1), 01007 (2024). https://doi.org/10.21272/jnep.16(2).02004
G.P. Edmundo, K.R. Tanya, and R.N. Jonathan, “Design and Applications of Water-Soluble Coordination Cages,” Chem. Rev. 120, 13480−13544 (2020). http://dx.doi.org/10.1021/acs.chemrev.0c00672
S. Yi, J.-S. Chen, C.-M. Wang, and W.-S. Liao, “Manipulating Chemical Processes by Pseudosolid Spatial Limitation”, JACS Au, 1(9): 1435–1444 (2021). https://doi.org/10.1021/jacsau.1c00202
E. Guzmán, F. Martínez-Pedrero, C. Calero, A. Maestro, F. Ortega, and R.G. Rubio, “A broad perspective to particle-laden fluid interfaces systems: from chemically homogeneous particles to active colloids”, Advances in Colloid and Interface Science, 302, 102620 (2022). https://doi.org/10.1016/j.cis.2022.102620
N.F. Zikrillayev, S.B. Isamov, B.O. Isakov, T. Wumaier, L.W. Liang, J.X. Zhan, and T. Xiayimulati, “New Technological Solution for the Tailoring of Multilayer Silicon-based Systems with Binary Nanoclusters Involving Elements of Groups III and V,” J. Nano- Electron. Phys. 15, 06024 (2023). https://doi.org/10.21272/jnep.15(6).06024
X.M. Iliyev, S.B. Isamov, B.O. Isakov, U.X. Qurbonova, and S.A. Abduraxmonov, “A surface study of Si doped simultaneously with Ga and Sb,” East European Journal of Physics, (3), 303-307 (2023). https://doi.org/10.26565/2312-4334-2023-3-29
X.M. Iliyev, V.B. Odzhaev, S.B. Isamov, B.O. Isakov, B.K. Ismaylov, K.S. Ayupov, and Sh.I. Hamrokulov, “X-ray diffraction and Raman spectroscopy analyses of GaSb-enriched Si surface formed by applying diffusion doping technique,” East Eur. J. Phys. (3), 363-369 (2023), https://doi.org/10.26565/2312-4334-2023-3-38
Kh.M. Iliev, S.V. Koveshnikov, B.O. Isakov, E.Zh. Kosbergenov, G.A. Kushiev, and Z.B. Khudoynazarov, “The Elemental Composition Investigation of Silicon Doped with Gallium and Antimony Atoms,” Surface Engineering and Applied Electrochemistry, 60(4), 633–639 (2024). https://doi.org/10.3103/S106837552470025X
S.K. Madisetti, V. Tokranov, A. Greene, S. Novak, M. Yakimov, S. Oktyabrsky, S. Bentley, and A.P. Jacob, “GaSb on Si: Structural Defects and Their Effect on Surface Morphology and Electrical Properties,” Mater. Res. Soc. Symp. Proc. 1635, (2014). https://doi.org/10.1557/opl.2014.219
J. Gebauer, M. Lausmann, F. Redmann, R. Krause-Rehberg, H.S. Leipner, E.R. Weber, and Ph. Ebert, “Determination of the Gibbs free energy of formation of Ga vacancies in GaAs by positron annihilation,” Physical Review B, 67, 235207 (2003), https://doi.org/10.1103/PhysRevB.67.235207
Shuo Liu, Chaochao Dun, Jeffrey J. Urban, Mark T. Swihart, “Non-Equilibrium Synthesis Methods to Create Metastable and High-Entropy Nanomaterials,” Advanced Science, 13, e21953 (2026). https://doi.org/10.1002/advs.202521953
A. Orlando, F. Franceschini, C. Muscas, S. Pidkova, M. Bartoli, M. Rovere, and A. Tagliaferro, “A Comprehensive Review on Raman Spectroscopy Applications,” Chemosensors, 9, 262 (2021). https://doi.org/10.3390/chemosensors9090262
X. Cong, X.-L. Liu, M.-L. Lin, and P.-H. Tan, “Application of Raman spectroscopy to probe fundamental properties of two-dimensional materials,” npj 2D Materials and Applications, 13, (2020). https://doi.org/10.1038/s41699-020-0140-4
G. La Penna, C. Mancini, A. Proietti, L. Buccini, D. Passeri, N. Gambacorti, J. Richy, and M. Rossi, “Strained Silicon Technology: Non-Destructive High-Lateral-Resolution Characterization Through Tip-Enhanced Raman Spectroscopy,” Applied Spectroscopy, 78(12) 1245–1255 (2024). https://doi.org/10.1177/00037028241246292
W. O’Leary, M. Grumet, W. Kaiser, T. Bucko, J.L. M. Rupp, and D.A. Egger, “Rapid Characterization of Point Defects in Solid-State Ion Conductors Using Raman Spectroscopy, Machine-Learning Force Fields, and Atomic Raman Tensors,” J. Am. Chem. Soc. 146, 26863−26876 (2024). https://doi.org/10.1021/jacs.4c07812
G. Gouadec, and P. Colomban, “Raman Spectroscopy of Nanomaterials: How Spectra Relate to Disorder, Particle Size and Mechanical Properties,” Progress in Crystal Growth and Characterization of Materials, 53(1), 1-56 (2007). https://doi.org/10.1016/j.pcrysgrow.2007.01.001
P.V. Pham, T.-H. Mai, S.P. Dash, V. Biju, Y.-L. Chueh, D. Jariwala, and V. Tung, “Transfer of 2D Films: From Imperfection to Perfection,” ACS Nano, 18, 14841−14876 (2024). https://doi.org/10.1021/acsnano.4c00590
G. Gyarmati, and J. Erdélyi, “Intermetallic Phase Control in Cast Aluminum Alloys by Utilizing Heterogeneous Nucleation on Oxides,” Metals, 15, 404 (2025). https://doi.org/10.3390/met15040404
S. Barth, M.S. Seifner, and S. Maldonado, “Metastable Group IV Allotropes and Solid Solutions: Nanoparticles and Nanowires,” Chem. Mater. 32, 2703−2741 (2020). https://dx.doi.org/10.1021/acs.chemmater.9b04471
A.P. Arun, N. Sreenivasan, J.H. Patil, R. Kusanur, H.L. Ramachandraiah, and M. Ramakrishna, “Thin Films for Next Generation Technologies: A Comprehensive Review of Fundamentals, Growth, Deposition Strategies, Applications, and Emerging Frontiers,” Processes, 13, 3846 (2025). https://doi.org/10.3390/pr13123846
A. Giunto, A. Fontcuberta i Morral, “Defects in Ge and GeSn and their impact on optoelectronic properties,” Appl. Phys. Rev. 11, 041333 (2024). https://doi.org/10.1063/5.0218623
J. Ponis, S. Hariyani, G. Agbeworvi, S. Chakraborty, V. Balcorta, J. Pérez-Vázquez, B.L. Rogers, et al., “Single Crystals of Vanadium Oxides as a Lens for Understanding Structural and Electronic Phase Transformations, Ion Transport, Chemo-Mechanical Coupling, and Electrothermal Neuronal Emulation,” Chem. Rev. 125, 10657−10764 (2025). https://doi.org/10.1021/acs.chemrev.5c00413
A. Zaitsev, N. Arutyunyan, and A. Koldaev, “Hot Ductility, Homogeneity of the Composition, Structure, and Properties of High-Strength Microalloyed Steels: A Critical Review,” Metals, 13, 1066 (2023). https://doi.org/10.3390/met13061066
A.A. Ilie, F. Niculescu, G. Iacob, I. Pencea, F. Miculescu, R. Bololoi, D.-V. Drăgut, et al., “Microstructure and Properties of Bi-Sn, Bi-Sn-Sb, and Bi-Sn-Ag Solder Alloys for Electronic Applications,” Metals, 15, 915 (2025). https://doi.org/10.3390/met15080915
W.-J. Moon, S.G. Yu, Y.S. Kim, B.-K. Park, W.-G. Jung, and H.-J. Song, “New strategy to improve the accuracy of quantitative analysis of energy dispersive spectroscopy,” Phys. Scr. 99, 035013, (2024). https://doi.org/10.1088/1402-4896/ad241e
M. Xie, M. Li, L. Li, J. Zhang, K. Jiang, L. Shang, Y. Li, et al., “Temperature-dependent phonon mode and interband electronic transition evolutions of e-InSe films derived by pulsed laser deposition,” Appl. Phys. Lett. 117, 102101 (2020). https://doi.org/10.1063/5.0021330
S. Marola, S. Bosia, A. Veltro, G. Fiore, D. Manfredi, M. Lombardi, G. Amato, et al., “Residual stresses in additively manufactured AlSi10Mg: Raman spectroscopy and X-ray diffraction analysis,” Materials and Design 202, 109550 (2021). https://doi.org/10.1016/j.matdes.2021.109550
M. Perez, M. Dumont, and D. Acevedo-Reyes, “Implementation of the classical nucleation theory for precipitation,” Acta Materialia, 56(9), 2119-2132 (2008). https://doi.org/10.1016/j.actamat.2007.12.050
W. Wełnic, and M. Wuttig, “Reversible switching in phase-change materials,” Materials today, 11(6), (2008). https://doi.org/10.1016/S1369-7021(08)70118-4
Copyright (c) 2026 Bobir O. Isakov, Khalmurat M. Iliev, Kutub S. Ayupov, Bakhram A. Abdurakhmanov, Giyosiddin A. Kushiev, Abdujalol A. Sattorov, Zafar B. Khudoynazarov
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